Stretchable laminates

ABSTRACT

The present invention provides stretchable laminates with a flat appearance on the visible surface. The laminates comprise a textile layer, a functional layer, and a plurality of elastic fibers. The plurality of elastic fibers are in a substantially parallel arrangement and the internal distance between adjacent fibers does not exceed the maximum fiber spacing, which depends on laminate thickness in a stretched state. Also provided are garments and footwear comprising the stretchable laminates and methods of producing the stretchable laminates.

PRIORITY CLAIM

This application is a national phase filing under 35 USC 371 ofInternational Application No. PCT/US2017/054888, filed Oct. 3, 2017,which claims priority to U.S. Provisional Application No. 62/403,805filed on Oct. 4, 2016, the entire contents and disclosure of which areincorporated herein by reference in their entirety.

TECHNICAL FIELD OF THE INVENTION

Generally, the present invention relates to stretchable laminates. Morespecifically, this invention relates to laminates of textile andfunctional layers having a flat appearance on the surface of the textileopposite the functional layer when the laminate is in a non-stretchedstate.

BACKGROUND OF THE INVENTION

Waterproof, vapor-permeable laminates with stretch characteristics arehighly desirable for incorporation into articles such as garments.Stretch characteristics are desired where flexibility of movement isneeded for the garment or to achieve a form-fitting garment. Withoutbeing tailor made, a form-fitting garment uses stretch characteristicsfor a closer fit without adversely affecting the wearer's comfort.Gloves, mittens, socks, stockings, ski wear, running suits, athleticgarments and medical compresses are some examples of such garments thatbenefit from form-fitting characteristics.

Currently, stretchability in waterproof applications may be achieved byusing elastic or stretch textiles laminated to a functional layer thatprovides waterproofness and vapor-permeability. The elastic or stretchtextiles may be made from elastic materials or are coated with anelastic material to impart stretch to the textile. By utilizing elasticor stretch outer textiles, these laminates are generally able to achievea flat surface appearance. For example, US Pub. No. 2009/0227165discloses a stretch composite fabric comprising a sintered expandedporous polytetrafluoroethylene film and a stretch cloth laminated toeach other while maintaining a flat state. US Pub. No. 2013/0291293discloses waterproof, breathable, stretch-recoverable composites thatare utilizable within footwear assemblies and exhibit stretchability inat least one direction by at least 35% at 4 lbs force and exhibit atleast 80% recovery.

U.S. Pat. No. 5,804,011 discloses a stretchable layered fabric laminatewhich is air impermeable and waterproof while being permeable to watervapor. The stretchable fabric laminate includes a stretchable compositematerial layer consisting of a hydrophobic protective layer of a porouspolymeric material on each side of a layer of hydrophilicwater-vapor-permeable synthetic polymer. The composite material layer islaminated to at least one layer of stretchable fabric. The stretchablelayered fabric laminate has excellent stretch and recovery properties inboth machine and transverse directions, and is useful for themanufacture of form-fitting articles of protective clothing and otherend uses. In addition, conventional stretchable laminates incorporatingnon-elastic textiles tend to have a rough or uneven appearance in thenon-stretched state, leading to poor aesthetics and low customeracceptance. For example, surface puckers increase the thickness of thelaminate and can make the laminate more bulky and difficult to wear orto incorporate in small applications, such as a shoe tongue. In thenon-stretched state or relaxed state, the outer surface of aconventional stretchable laminate incorporating non-elastic materialshas bunching, rippling, buckling, and/or puckering. U.S. Pat. No.6,713,415 discloses a laundry-durable unitary composite stretchablepuckered fabric and processes for producing the fabric, based on twononwoven outer layers and a pre-stretched inner layer of elastomericfibers of at least 400 decitex and at least eight threadlines/inch.

A variety of attempts have been made to improve stretchable, breathablelaminates. Although, improvements have been made, it has not beenpossible to create flat laminates incorporating non-elastic textilesthat are free from bunching, rippling, buckling, and/or puckering. Inaddition, many of these fabrics obtain varying degrees ofwaterproofness, breathability, stretch, stretch-recovery, and comfort.Continued efforts are needed, however, to provide the desired propertiesfor garments and/or footwear while having a surface that has anaesthetic appearance in a non-stretched state and expanding the types oftextiles, such as non-elastic or relatively inelastic textiles, that maybe used in stretchable laminates.

BRIEF SUMMARY OF THE INVENTION

In some embodiments, the disclosure relates to a stretchable laminatecomprising a textile layer comprising a non-elastic material having afirst surface and a second surface; a functional layer disposed on atleast one surface of the textile layer; and a plurality of elasticfibers, having an adjacent fiber spacing distance, disposed in asubstantially parallel arrangement on at least one of the textile and/orthe functional layer wherein at least 80% of the elastic fibers have anadjacent spacing that is less than the maximum fiber spacing, whereinthe maximum fiber spacing, in millimeters, is equal to or less than 3.0times the thickness of the stretchable laminate in a stretched state, inmillimeters; and wherein:

i) the plurality of elastic fibers are disposed between the textilelayer and the functional layer;

ii) the functional layer is disposed on the first surface of the textilelayer and the plurality of elastic fibers are disposed on a side of thefunctional layer opposite to the textile layer; or

iii) the functional layer is disposed on the second surface of thetextile layer and the plurality of elastic fibers is disposed on thefirst surface of the textile layer.

In other embodiments there is provided a stretchable laminate andgarments made therefrom comprising a textile layer comprising anon-elastic material having a first surface and a second surface; afunctional layer disposed on at least one surface of the textile layer;and a plurality of elastic fibers disposed in a substantially parallelarrangement on at least one of the textile layer and/or the functionallayer, wherein the surface of the textile layer opposite the functionallayer, in a non-stretched state, has an average normalized surfaceroughness (Ra) of less than or equal to 25 micrometers, wherein:

i) the plurality of elastic fibers are disposed between the textilelayer and the functional layer;

ii) the functional layer is disposed on the first surface of the textilelayer and the plurality of elastic fibers are disposed on a side of thefunctional layer opposite to the textile layer; or

iii) the functional layer is disposed on the second surface of thetextile layer and the plurality of elastic fibers is disposed on thefirst surface of the textile layer.

In some embodiments, the maximum distance between adjacent fibers doesnot exceed the maximum fiber spacing of the stretchable laminate. Insome embodiments, the surface of the textile opposite the functionallayer is substantially free of buckling or non-uniform buckling.

In another embodiment the elastic fibers may be disposed in asubstantially parallel arrangement between two functional layers, withor without textile layer(s), wherein the surface of the functional layeropposite the plurality of elastic fibers is substantially free ofbuckling. In other embodiments, a stretchable laminate comprises aplurality of elastic fibers disposed in a substantially parallelarrangement on a first functional layer and optionally furthercomprising a second functional layer wherein the second functional layeris disposed on the first functional layer with the elastic fibersdisposed between the first and second functional layers or wherein thesecond functional layer is disposed on the first functional layer on theside opposite the plurality of elastic fibers; and wherein the pluralityof elastic fibers have a fiber density, or spacing of fibers, of atleast 7.9 fibers per centimeter, e.g., at least 8.0 fibers percentimeter or at least 10.0 fibers per centimeter. In some embodiments,a stretchable laminate may comprise a textile layer comprising amaterial having a first surface and a second surface; a plurality ofelastic fibers disposed in a substantially parallel arrangement betweena first functional layer and a second functional layer, where the firstfunctional layer or the second functional layer is disposed on the firstsurface of the textile layer.

In yet another embodiment the elastic fibers may be disposed in asubstantially parallel arrangement on a side of the functional layer,specifically, on the opposite side of the functional layer from thetextile layer. In some embodiments, a stretchable laminate comprises atextile layer comprising a material having a first surface and a secondsurface; and a functional layer having a plurality of elastic fibersdisposed in a substantially parallel arrangement disposed on a side ofthe functional layer, wherein the functional layer is disposed betweenthe textile layer and the plurality of elastic fibers.

In further embodiments the elastic fibers may be disposed in asubstantially parallel arrangement on the first surface of the textilelayer, and the functional layer disposed on the second surface of thetextile. The stretchable laminate comprises a textile layer comprising amaterial having a first surface and a second surface; a plurality ofelastic fibers disposed in a substantially parallel arrangement on thefirst surface of the textile layer; and a functional layer disposed onthe second surface of the textile layer.

In still further embodiments the functional layer or the textile layermay be omitted. In one such embodiment, stretchable laminate maycomprise a textile layer comprising a material having a first surfaceand a second surface; a plurality of elastic fibers disposed in asubstantially parallel arrangement on the first surface of the textilelayer. In other embodiments, the textile layer may be omitted. Inanother embodiment, a stretchable laminate may comprise a functionallayer; wherein a plurality of elastic fibers is disposed in asubstantially parallel arrangement on a surface of the functional layer,wherein the plurality of elastic fibers have an internal distance thatis less than or equal to the maximum fiber spacing based on the laminatethickness, as measured in the stretch state. In some embodiments, thefiber density is at least 7.9 fibers per centimeter.

In some embodiments, the denier of the elastic fibers is 400 denier orless. In some cases, the denier is 300 denier, 200 denier, 150 denier,or a denier less than 150 denier or less, as described herein. In someexamples, the functional layer has a thickness that is less than 0.06mm, e.g., less than 0.05 mm, less than 0.04 mm, or less than 0.03 mm.

In another embodiment there is provided garments comprising thelaminates disclosed herein. In one embodiment, the laminate is used inan elbow panel, a shoulder region, a side panel, or a shoe tongue.

BRIEF DESCRIPTION OF THE DRAWINGS

The advantages of this invention will be apparent upon consideration ofthe following detailed disclosure of the invention, especially whentaken in conjunction with the accompanying drawings wherein:

FIG. 1A is a photograph of a stretchable laminate having a flatappearance in a non-stretched state according to embodiments of thepresent invention. FIG. 1B is a photograph of a stretchable laminatehaving a buckled surface in a non-stretched state.

FIG. 2 is a schematic representation of a cross-section of a stretchablelaminate having a flat surface in a non-stretched state according toembodiments of the present invention.

FIG. 3 is a perspective view of uniformly spaced fibers on a functionallayer according to embodiments of the present invention.

FIG. 4 is a schematic representation of a cross-section of a stretchablelaminate having a flat surface in a non-stretched state according toembodiments of the present invention.

FIG. 5 is a schematic representation of a cross-section of a stretchablelaminate having a flat surface in a non-stretched state according toembodiments of the present invention.

FIG. 6 is a schematic representation of a cross-section of a stretchablelaminate having a flat surface in a non-stretched state according toembodiments of the present invention.

FIG. 7 is a schematic representation of a cross-section of a stretchablelaminate having a flat surface in a non-stretched state according toembodiments of the present invention.

FIG. 8 is a schematic representation of a cross-section of a stretchablelaminate having a flat surface in a non-stretched state according toembodiments of the present invention.

FIG. 9 is a schematic representation of a stretchable laminatesincorporated into a garment.

FIG. 10A is a photograph of a woven fabric with an arrow indicatingfeature spacing.

FIG. 10B is a photograph of a knit fabric with an arrow indicatingfeature spacing.

FIG. 11A is a 3-dimensional surface plot of a stretchable laminate ofthe present invention.

FIG. 11B is a graph of normalized surface roughness (Ra) measurementsacross the surface of a stretchable laminate of the present invention.

FIG. 12A is a 3-dimensional surface plot of a comparative stretchablelaminate with a buckled surface due to improper elastic fiber spacing.

FIG. 12B is a graph of normalized Ra measurements across the surface ofa stretchable laminate with a buckled surface.

FIG. 13A is a 3-dimensional surface plot of a stretchable laminate ofthe present invention.

FIG. 13B is a graph of normalized surface roughness (Ra) measurementsacross the surface of a stretchable laminate of the present invention.

FIG. 14A is a 3-dimensional surface plot of a comparative stretchablelaminate with a buckled surface due to improper elastic fiber spacing.

FIG. 14B is a graph of normalized Ra measurements across the surface ofa stretchable laminate with a buckled surface.

FIG. 15A is a 3-dimensional surface plot of a comparative stretchablelaminate with a buckled surface due to improper elastic fiber spacing.

FIG. 15B is a graph of normalized Ra measurements across the surface ofa stretchable laminate with a buckled surface.

FIG. 16A is a 3-dimensional surface plot of a stretchable laminate ofthe present invention.

FIG. 16B is a graph of normalized surface roughness (Ra) measurementsacross the surface of a stretchable laminate of the present invention.

FIG. 17 is a table of properties of laminates of the invention andcomparative laminates.

FIG. 18 is a graph of laminate thickness vs. fiber spacing andcorrelates fiber spacing to normalized Ra values.

DETAILED DESCRIPTION OF THE INVENTION

Disclosed are stretchable laminates and in some embodiments stretchablelaminates having a flat appearance in a non-stretched state. In general,the stretchable laminates of the present invention comprise a textilelayer and/or a functional layer, and a plurality of elastic fibers.Incorporating elastic fibers separate from the textile layer, which maybe a non-elastic textile layer, provides for stretchable laminates. Thestretchable laminates have elasticity in the direction of the elasticfibers. Several arrangements of the layers described herein are alsowithin the scope of the present invention. In addition, other layers,such as adhesive layers or backing layers, may be incorporated into thestretchable laminates of the present invention.

In some embodiments, the present disclosure provides stretchablelaminates comprising a textile layer comprising a material having afirst surface and a second surface, a functional layer disposed on atleast one surface of the textile layer, and a plurality of elasticfibers disposed in a substantially parallel arrangement on at least oneof the textile layer and/or the functional layer. In some embodiments,the plurality of elastic fibers are disposed between the textile layerand the functional layer. In other embodiments, the functional layer isdisposed on the first surface of the textile layer and the plurality ofelastic fibers are disposed on a side of the functional layer oppositethe textile layer. In still further embodiments, the functional layer isdisposed on the second surface of the textile layer and the plurality ofelastic fibers is disposed on the first surface of the textile layer. Inother embodiments, the present disclosure provides stretchable laminatescomprising a plurality of elastic fibers disposed in a substantiallyparallel arrangement on a first functional layer; optionally furthercomprising a second functional layer wherein the second functional layeris disposed on the first functional layer with the elastic fibersdisposed between the first and second functional layers or wherein thesecond functional layer is disposed on the first functional layer on theside opposite the plurality of elastic fibers; and wherein the pluralityof elastic fibers have a fiber density of at least 7.9 fibers percentimeter. The second functional layer may be chosen independently fromthe first functional layer and can be chosen from the same materials asdisclosed for the first functional layer. In still further embodiments,the present disclosure provides a stretchable laminate comprising afirst textile layer having a first surface and a second surface, asecond textile layer disposed on at least one surface of the firsttextile layer, and a plurality of elastic fibers disposed in asubstantially parallel arrangement between the first and second textilelayers or disposed on at least one of the first or second textilelayers. For the purposes of this invention, “on” is intended mean thatat least a portion of one layer, for example, the textile layer, coversat least a portion of the adjacent layer, for example, the functionallayer.

Advantageously, the embodiments of the present invention may provide aflat appearance on the textile surface of the laminate opposite thefunctional layer leading to an aesthetic appearance. This eliminatesundesired bunching, rippling, buckling, and/or puckering on the surfacewhich detracts from the aesthetic appearance. In particular forform-fitting garments, the flat appearance is particularly appealing. Aflat appearance refers to the textile surface of the laminate oppositethe functional layer. In some garment embodiments, this is the surfaceof the laminate which is facing the environment and is not next to thewearer, where the texture of the textile is visible without introducingareas of non-conformity that causes undesired bunching, rippling,buckling, and/or puckering on the surface. In other garment embodiments,the functional layer may be the outer layer which is facing theenvironment and is not next to the wearer. In embodiments where thefunctional layer is the layer facing the environment, the textilesurface may be an inner layer, that is adjacent the skin or otherclothing of the wearer without introducing bunching, rippling, buckling,and/or puckering on the surface which may cause an unpleasant sensorialfeel to the wearer. Bunching, rippling, buckling, and/or puckering, forthe purposes of this disclosure, are non-conformities that causeundulations on the surface of the textile that is opposite thefunctional layer that are different from the texture of the textilelayer prior to the formation of the laminate. For instance, FIG. 1A isan exemplary laminate according to the embodiments of the presentinvention where the surface of the textile layer opposite the functionallayer has no visible buckling, whereas a laminate having unacceptablebuckling is shown in FIG. 1B. As described herein, the buckling in FIG.1B is caused by the inadequate arrangement of the elastic fibers.Embodiments of the present invention achieve a flat appearance byproviding an arrangement of elastic fibers that does not cause bunching,rippling, buckling, and/or puckering on the surface of the textile layerthat is opposite the functional layer.

Determining a flat appearance may vary depending on the type of textileand the layers of the laminate. In general, each textile has a naturalsurface texture. The laminates described herein achieve a flatappearance that does not significantly alter the natural surface textureof the textile, for example, the natural surface texture of the textileprior to the formation of the laminate. In one embodiment, the surfaceof the textile layer opposite the functional layer in a non-stretchedstate has an average normalized surface roughness (Ra) of less than orequal to 25 micrometers, e.g., less than or equal to 20 micrometers,less than or equal to 15 micrometers, less than or equal to 10micrometers, or less than or equal to 5 micrometers. In terms of ranges,the average normalized Ra may be from 1 to 25 micrometers, e.g., from 5to 25 micrometers, or from 10 to 20 micrometers. By having an averagenormalized Ra of less than or equal to 25 micrometers, the textilesurface is substantially free of buckling and other non-conformities,for example, puckering. In some embodiments, the maximum normalizedsurface roughness (Ra) is no more than 50% larger than the averagenormalized surface roughness (Ra). In other embodiments, the surface ofthe textile layer has a maximum normalized surface roughness (Ra) ofless than or equal to 25 micrometers.

The flatness of a surface can be assessed by profilometery. Briefly,profilometery measures the surface topography of a laminate swatch. Thesurface topography measurement may be normalized to account for thenatural surface roughness of the textile layers. The normalized surfaceroughness (Ra) may then be calculated from the normalized surfacetopography data. For instance, a tweed or fleece may have a naturalsurface roughness with more texture than a plain weave nylon. Thenormalized Ra uses a filter window of two feature lengths as describedin the test procedures. When the normalized Ra becomes greater than 25micrometers the occurrence of non-conformities increases, which leads toa non-flat appearance and poor aesthetics. As used herein, the phrase“substantially free of buckling” means that the normalized Ra is lessthan or equal to 25 micrometers.

As shown in FIG. 2 , laminate 1 comprises a textile layer 10, pluralityof elastic fibers 20 and a functional layer 40. The textile layer 10 hasa first surface 11 and a second surface 12. The second surface 12 is thesurface that is opposite the functional layer 40. A functional layer 40is disposed on the first surface 11 of the textile layer 10. Between thetextile layer 10 and functional layer 40 there is disposed a pluralityof elastic fibers 20. Each of the elastic fibers 20 are disposed in asubstantially parallel arrangement with respect to each other and havean internal spacing of d. An adhesive layer 30 is disposed between thefunctional layer 40 and the plurality of elastic fibers 20. Adhesivelayer 30 also bonds the textile layer 10 to the functional layer 40. Thethickness of the laminate 1 may vary depending on the textile layer 10and number of layers. As discussed herein the internal distance dbetween elastic fibers 20 may be dependent upon on the thickness of thelaminate 1. In some embodiments, the thickness of the laminate 1 in astretched state is from 0.05 to 4 millimeters, e.g., from 0.1 to 2 mm,or from 0.1 to 1 mm.

The present invention may be useful for laminates 1 that incorporatetextile layers 10 that are made of non-elastic or relatively inelasticmaterials. In some embodiments, the laminates 1 may incorporate textileshaving elastic materials and the elastic fibers 20 may further increasethe elasticity of the laminate 1. Non-elastic materials may includematerials that are not coated with an elastic material, or that do notcomprise elastic materials woven or knitted into the textile layer.Thus, in some embodiments, the material of the textile layer 10 isuncoated and is unfilled with any elastomer or other material that wouldimpart elasticity. In one embodiment, the material of textile layer 10has an elasticity that is less than the elasticity of the elastic fibers20. For example, the elastic fibers may have an elasticity that is atleast 1.5× greater than the textile layer, e.g., at least 2×, at least3× or at least 4×. In certain embodiments, textile layer 10 may be madeof a non-elastic material so that textile layer 10 independent of thestretch characteristics of the laminate 1 has an elongation of less thanor equal to 15%, as measured according to ASTM test method D 5035-06. Inother embodiments, the elongation of the textile layer may be less thanor equal to 10%, or less than or equal to 5%.

Textile layer 10 may be a woven layer, knitted layer, or non-wovenlayer. The term “woven” may include any textile structure made up withweft and warp yarns or filaments. The term “knit” is to be understoodbroadly, in particular including any forms of warp knits and circularknits, but also covering any other configurations where a textilestructure is produced by wrapping one or more yarns or filaments such asto form loops. Thus, a knit as used herein may also cover configurationsthat might be referred to as braided structures. As shown in FIG. 2 ,textile layer 10 is a woven layer. In some embodiments, textile layer 10may be a woven layer or knitted layer. Depending on the pattern, knittedlayers may inherently have some stretch, but may still be made ofnon-elastic materials. Knitted materials may be knitted from yarns thatare non-elastic yarns, or from yarns that do not comprise an elasticcoating. In some embodiments, a second or subsequent textile layer maybe used, wherein each second or subsequent textile layer isindependently chosen from the textile layers given above.

In some embodiments, the material of the textile layer 10 may be anatural fiber, or polymer fibers, or a blend of these fibers. Naturalfibers include, for example, cotton, silk, cellulose, and/or wool.Polymer fibers include, for example, polyamides, polyolefins,polyacrylates, polyesters, polyurethanes, fluoropolymers, and copolymersthereof. In some embodiments, at least a portion of the material of thetextile layer 10 can be a flame or fire retardant textile material, forexample, aromatic polyamides, NOMEX® poly-metaphenylene isophthalamide,flame resistant (FR) cotton, polybenzimidazole (PBI), polybenzoxazole(PBO), FR rayon, modacrylic, modacrylic blends, carbon fibers,fiberglass, polyacrylonitrile, polytetraflurorethylene and blendsthereof. In some embodiments, the textile layer 10 is a polyester orpolyamide, such as a nylon. The material weight of the textile layer 10may vary from 15 and 500 grams/square meter (g/m²), or any materialweight between 15 and 500 g/m². In other embodiments, the materialweight of the textile layer can be 15, 16, 17, 18, 19, 20, 25, 30, 35,40, 45 or 50 and up to 400, 425, 450, 475 or 500 g/m². In otherembodiments, lighter or heavier weight materials may also be used. Thethickness of the textile layer 10 may also vary and is generally from0.05 to 4 mm, e.g., from 0.1 to 2 mm, or from 0.1 to 1 mm.

In some embodiments, there may be an abrasion coating on the surface 12of the textile layer 10 that is opposite the functional layer. Theabrasion coating may be continuous or discontinuous. In certainembodiments, the abrasion coating may comprise one or more layers ofsilicone, polyamide, polyester, epoxy, polyolefin or polyurethane. Theabrasion coating may be applied in a manner that does not impair thewaterproofness and breathability of the laminate 1.

The functional layer 40 can be used to impart breathability and allowmoisture vapor transmission while providing water impermeability. In oneembodiment, the functional layer 40 may be a porous membrane ornon-porous membrane. In another embodiment, the functional layer 40could be a barrier to chemical gases, liquids and/or particulate. A“membrane” as used herein is a barrier or film permeable to water vaporor moisture, but having waterproof characteristics. In some embodiments,the membrane has undergone further processing, such as surface coatings,imbibed coatings, node and fibril coatings, etc., and may also bereferred to as a film. The membrane or film is considered to havewaterproof characteristics in cases where the requirements specified inDIN EN 343 (2010) are met, i.e. a test of the liquid water resistancewith respect to hydrostatic water pressure according to EN 20 811 (1992)yields a liquid water resistance (Wp) of 8000 Pa, or more.

In some embodiments, the functional layer 40 and any second orsubsequent functional layer, if present, comprises at least one of apolyurethane, a copolyether-ester, a polyolefin, a polyester, afluoropolymer, or a combination thereof. Suitable fluoropolymersinclude, for example, polytetrafluoroethylene (PTFE), polyvinylidenefluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer(FEP), and tetrafluoroethylene-(perfluoroalkyl) vinyl ether copolymer(PFA). In some embodiments, the functional layer(s) may be an expandedpolytetrafluoroethylene (ePTFE) membrane. Porous membranes that can beused include, for example, one or more layers of ePTFE membrane made inaccordance with U.S. Pat. No. 7,306,729 by Bacino et al., U.S. Pat. No.3,953,566 by Gore, U.S. Pat. No. 5,476,589 by Bacino, U.S. Pat. No.5,183,545 by Branca et al., U.S. Pat. No. 4,902,423 Bacino, each ofwhich is incorporated by reference in its entirety. In certainembodiments, the functional layer(s) may include a copolymer oftetrafluoroethylene (TFE) and one or more monomers is vinylidenedifluoride (VDF), hexafluoropropylene (HFP), chlorotrifluoroethylene(CTFE), ethylene, vinylidene fluoride (VF), perfluoroalkoxy (PFA),perfluoroether, and trifluoroethylene, or combinations thereof.Alternatively, functional layer 40 may comprise a monolithic membrane,in particular made from a hydrophilic polymer, like polyurethane and/oror polyether-polyester. In some embodiments, the stretchable laminatescan comprise a second or subsequent functional layer wherein each secondor subsequent functional layer can be independently chosen from thefunctional layers given above.

Similar to the textile material, some of the functional layers 40 mayhave an elasticity less than the elasticity of the elastic fibers 20. Inparticular ePTFE may have relatively inelastic characteristics. Althoughthe elasticity of the functional layer 40 that used ePTFE may beimproved by imbibed elastomers, this requires an additional step to makethe functional layer 40. Further, the imbibing process is not necessaryand the embodiments can use functional layers 40 regardless of whetheran elastomer has been imbibed therein.

To achieve good water vapor permeability while still providingsufficiently waterproof characteristics, in some embodiments, thefunctional layer can be a porous membranes having a mean flow pore sizefrom 0.05 μm to 0.5 μm, particularly from 0.1 μm to 0.5 μm; and moreparticularly from 0.2 μm to 0.45 μm. In other embodiments, thefunctional layer may be a breathable polyurethane film, in which casethere is no porosity. In still other embodiments, the functional layercould be both non-breathable and non-porous, such as in a chemicalbarrier application that is useful for industrial or military gradegarments.

When a functional layer 40 is incorporated into the laminate, thelaminate may have a Moisture Vapor Transmission Rate (MVTR) according toDIN EN ISO 15496 (2004) of at least 3000 g/m²/24 hr, e.g., at least 6000g/m²/24 hr, at least 8000 g/m²/24 hr, or at least 12000 g/m²/24 hr, andmay have a range from 3000 to 20000 g/m²/24 hr. To maintain acceptableMVTR, in some embodiments, the elastic fibers 20 cover less than orequal to 40% of the surface area of the functional layer 40, e.g., lessthan or equal to 20%. Lower surface coverage can avoid a significantdecrease in MVTR.

The functional layer 40 is typically a very thin layer. In oneembodiment, the thickness of the functional layer 40 is from 0.01 to 0.5mm, e.g., from 0.01 to 0.3 mm. In some embodiments, the functional layerhas a thickness that is less than 0.06 mm, less than 0.05 mm, less than0.04 mm, or less than 0.03 mm.

Additional treatments may be provided that impart functionality, such asbut not limited to, oleophobicity and hydrophobicity. In someembodiments, the membrane can be treated with an oleophobic and/orhydrophobic coating. Examples of oleophobic coatings include forexample, polyurethanes, fluoropolymers such as fluoroacrylates and othermaterials such as those taught in U.S. Pat. No. 6,261,678, and U.S. Pub.No. 2007/0272606, the entire contents and disclosures of which areincorporated by reference. Oleophobicity can also be provided by coatingat least one surface of the membrane with a continuous coating of anoleophobic, moisture vapor transmissive polymer.

Turning to the elastic fibers 20, which are added as a separate layer tothe laminate 1 in a substantially parallel arrangement, the elasticfibers 20 have a recovery of at least 80% when under a strain of atleast 20%, e.g. a strain of at least 50%, or a strain of at least 100%strain. In some embodiments, the recovery of the elastic fibers may behigher than 80%, and may be at least 90% or at least 95% under strainsof at least 20% or at least 50% or at least 100%. In certainembodiments, the elastic fibers 20 comprise at least one of anelastomer, such as natural rubber, polybutadiene, an elastomericpolyolefin, a polyurethane, a polyester, a silicone, a fluoroelastomer,an elastane, a block co-polymer containing polyesters, apolyester-polyurethane, a polyamide, or a combination thereof. In someembodiments, the elastic fibers 20 are elastane fibers, spandex, LYCRA®polyester-polyurethane fibers or a combination thereof. In someembodiments, the plurality of elastic fiber can be or can contain atleast a portion of elastomers that are flame or fire retardant, forexample, silicone elastomers or other fibers that have been treated witha known fire retardant additive or coating. In some embodiments, theplurality of elastic fibers 20 comprise a material that is differentthan the material of the textile layer 10. The denier of the elasticfibers 20 may be less than or equal to 400, 300, 200, 120, 100, or anyvalue therein. In one exemplary embodiment, the denier of the elasticfibers 20 is 300. In certain embodiments, the denier and/or weight ofthe elastic fibers 20 is matched to the material weight of the textilelayer, with heavier weight fabrics requiring a larger denier elasticfiber. The size of the elastic fiber may also depend on the in-planetextile compressibility, where the highly compression resistant textilegenerally use larger denier elastic fibers. In some embodiments, theelastic fibers have a weight from 30 to 400 denier, or any valuetherein, e.g., 40 to 300 denier, 50 to 200 denier, or 60 to 150 denier.The elastic fibers may be monofilament elastic fibers or multifilamentelastic fibers.

Uniform elastic fiber spacing may advantageously achieve a flatappearance on the surface of the laminate that is opposite thefunctional layer, which is typically the textile layer. FIG. 3 is aperspective view of FIG. 2 without the textile layer to show the uniformelastic fiber 20 spacing d in the longitudinal direction. The elasticfibers generally run in one direction, such as the longitudinaldirection of the fabric, and are substantially parallel to each other,though the fibers may occasionally contact or cross each other.

The internal distance d is the space between adjacent elastic fibers 20and is also referred to herein as the adjacent spacing. Not intending tobe bound by theory, when the internal distance between any two adjacentelastic fibers 20 exceeds a maximum distance determined primarily by thelaminate thickness, the outmost surface 12 of the laminate 1 tends tobuckle, ripple, bunch, and/or pucker. To avoid the undesired buckling,rippling, bunching, and/or puckering, a majority of the elastic fibers20 have an adjacent spacing that is less than or equal to the maximumfiber spacing (MFS). MFS in millimeters (mm) may be approximated by thefollowing formula:MFS=3(t)where t is the thickness of the laminate in mm, measured in a stretchedstate by tensioning the laminate to its fullest non-plastic extensionusing the procedure found in the examples section. In other embodiments,MFS in millimeters can be equal to 2.9(t) or 2.8(t) or 2.7(t) or 2.6(t)or 2.5(t) or 2.4(t) or 2.3(t) or 2.2(t) or 2.1(t) or 2.0(t), wherein tis the thickness of the laminate as measured in the stretched state. Insome embodiments, at least 80% of the elastic fibers have an adjacentspacing that is less than or equal to the MFS which is based on thethickness of the laminate as disclosed above. In other embodiments, atleast 85%, at least 90%, or 91° A or 92% or 93% or 94% or 95% or 96% or97% or 98% or 99% or 100% of the elastic fibers have an adjacent spacingthat is less than or equal to the MFS based on the thickness of thelaminate. In still further embodiments, the maximum distance betweenadjacent fibers does not exceed the maximum fiber spacing of thestretchable laminate. When 20% or more of the elastic fibers have anadjacent spacing that is greater than the MFS, non-uniformities mayoccur which lead to undesired buckling. This also causes the normalizedRa to have peaks above 25 micrometers.

The internal distance d between elastic fibers 20 depends on the MFS andcan vary with textile materials and thickness. In some embodiments, theplurality of elastic fibers are spaced apart at an internal distancefrom 0.1 to 1.5 millimeters (mm). In exemplary embodiments, the elasticfibers are uniformly spaced apart within a MFS that is less than orequal to 1.5 mm, e.g., less than or equal to 1.1 mm, less than or equalto 1 mm, less than or equal to 0.9 mm, less than or equal to 0.5 mm, orless than or equal to 0.4 mm. In terms of ranges, in certainembodiments, the MFS may be from 0.1 to 1.5 mm, e.g., from 0.25 to 1.1mm, 0.25 to 1 mm, 0.4 to 1 mm, 0.5 to 1 mm, or from 0.5 to 0.9 mm. Thisspacing of the elastic fibers allows for 5 to 40 elastic fibers perlinear centimeter of laminate in the transverse direction, i.e.direction perpendicular to the fibers. In some embodiments, the numberof elastic fibers per linear centimeter may be from 10 to 30 or from 15to 20.

The stretchable laminates further comprise an adhesive layer 30. As usedherein, the phrase “adhesive layer” means a bonding layer or region. Insome embodiments an adhesive composition is used to bond the layersand/or the elastic fibers. In other embodiments, the layers and/or theelastic fibers can be joined using other known bonding technique, suchas welding, etc. An adhesive layer is disposed between the plurality ofelastic fibers and the textile layer and/or the functional layer, andthe adhesive layer is typically used to join the textile or functionallayer to the next layer and/or one textile or functional layer to theplurality of elastic fibers. For example, if a stretchable laminatecomprising the textile layer/elastic fiber/functional layer compositestructure of FIG. 2 is desired, one adhesive layer can be used to bondthe textile layer to a plurality of elastic fibers and also to thefunctional layer, thus producing the desired stretchable laminate. Asshown in FIG. 2 adhesive layer 30 is disposed between the functionallayer 40 and the plurality of elastic fibers 20. In some embodiments,the plurality of elastic fibers 20 are adhered to the functional layer40 on the side opposite to the textile layer 10. In other embodiments,adhesive layer 30 is positioned so that the plurality of elastic fibers20 are first adhered to the textile layer 10 before being adhered to thefunctional layer 40. Depending on the arrangement of the layers theremay be multiple adhesive layers.

Any suitable adhesive composition may be used with the embodimentsdescribed herein. In some embodiments, the adhesive layer comprises anadhesive composition of polyurethane and styrene-based block copolymerssuch as styrene/isoprene and styrene/butadiene block copolymers, orcombinations thereof. In other embodiments, the adhesive composition cancomprise a flame or fire resistant additive as is known in the art. Inother embodiments, the adhesive composition can comprise an intumescentcarbon/polymer mixture, for example, as described in US 2013/0156680,which is incorporated by reference in its entirety.

The adhesive composition may be applied by any method known in the art,such as printing, spraying, stamping, or rolling; and in any pattern,such as lines, dots, or continuous area. In some embodiments, theplurality of elastic fibers 20 are adhered by a discontinuous layer ofadhesive 30 as shown in FIG. 3 . Adhesive dots having a diameter from100 to 1000 microns may be used. In embodiments where the adhesive layeris discontinuous, the spacing between adjacent adhesive areas whenmeasured from edge to edge is generally equal to or less than the MFS.“Edge to edge” when used in this context means the measurement of thedistance between two adjacent adhesive areas (i.e., the space thatcontains no adhesive material). In some embodiments, the edge to edgedistance is 100% or less than the MFS. In other embodiments, the edge toedge distance is less than 80% or less than 70% or less than 60% or lessthan 50% or less than 40% or less than 30% or less than 20% or less than10% of the MFS. It has been found that as the edge to edge spacingbetween adjacent adhesive areas approaches the MFS, then the surface ofthe laminate in a non-stretched state becomes less flat. In otherembodiments, the plurality of elastic fibers are adhered by a continuouslayer of adhesive as shown in FIG. 2 .

The total weight of the adhesive composition is less than or equal to35% of the total weight of the laminate, e.g., less than or equal to30%, less than or equal to 25%, less than or equal to 15%, less than orequal to 10%, or less than or equal to 5%. In some embodiments, thefunctional layer and the adhesive layer may be pre-associated in afunctional/adhesive layer. In one embodiment, the functional/adhesivelayer is a polyurethane-coated ePTFE. In other embodiments, the elasticfibers 20 and the adhesive layer 30 may be pre-associated by coating orprinting the adhesive layer onto the elastic fibers.

In other embodiments, no adhesive layer is used and the layers may bewelded or otherwise bonded together by compression.

Optionally, the stretchable laminate may comprise a backing layer, forexample, a second textile layer or a second functional layer. In someembodiments, the backing layer may comprise a woven, nonwoven or knittedmaterial. In other embodiments, the backing layer comprises at least oneof a woven, nonwoven or knitted nylon, polyester, cotton, silk, or acombination thereof. In other embodiments, the backing layer maycomprise one or more additional microporous layers. In some embodiments,the stretchable laminate further comprises a second textile layercomprising a non-elastic material having a first surface and a secondsurface, wherein the first surface of the second textile is disposed ona first or a second functional layer, if two functional layers areutilized. If a backing layer or a second textile layer is used, one orboth of the outwardly facing surfaces of the first and second textiles,that is, the surfaces that are opposite the functional layer, in anon-stretched state can have an average normalized surface roughness(Ra) of less than or equal to 25 micrometers.

Once assembled, the stretchable laminate 1 of FIG. 2 has a flatappearance that can achieve a desired aesthetic appearance. The flatappearance may be assessed by measuring the stretchable laminate in thenon-stretched state by profilometry as described herein. Also a majorityof the elastic fibers 20 of the stretchable laminate 1 of FIG. 2 arespaced by an internal distance d that is less than or equal to the MFS.Advantageously, by incorporating the elastic fibers into the stretchablelaminate the embodiments of the present invention can achieve a flatappearance and provide a stretchable laminate. The stretchable laminatemay have elasticity that is greater than the elasticity of the textilematerial prior to incorporation into the stretchable laminate. In oneembodiment the stretchable laminate has a recovery of at least 80% afteran elongation of at least 10%. In other embodiments, the stretchablelaminate has a recovery of at least 80% after an elongation of least20%, or an elongation of at least 25%, or an elongation of at least 50%.The textile materials and the functional layers used to produce thestretchable laminate can have an elongation of less than or equal to 15%or less than or equal to 10% or less than or equal to 5% as measured byASTM D 5035-06. The disclosed stretchable laminates can have anelongation of up to 150%, for example, greater than 5% or greater than10% or greater than 15% or in the range of from 5% to 150% as measuredby ASTM D 5035-06. In each case, the percentage elongation in thelaminate is greater than the elongation of any of the individual layersalone. In other embodiments, the stretchable laminates can have anelongation of 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%,65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, 105%, 110%, 115%, 120%, 125% orany value between any of those stated elongation values. Depending uponthe choice of the functional layer, the stretchable laminate can also bewaterproof and breathable in both the non-stretched and stretchedstates.

In addition to the arrangement shown in FIG. 2 , the embodiments mayalso have different arrangements of the layers with the elastic fibers.

FIG. 4 shows a laminate 2 having two functional layers 40, 42 and theplurality of elastic fibers 20 are disposed between the functionallayers 40, 42. A first adhesive layer 30 may bond the elastic fibers 20to one of the functional layers and may also bond the functional layers40, 42 together. A second adhesive layer 32 bonds one of the functionallayers 40 and the textile layer 10.

FIG. 5 shows a stretchable laminate 3 having a plurality of elasticfibers 20 disposed on a side of the functional layer 40 opposite of thetextile layer 10. A second adhesive layer 32 bonds the functional layer40 and the textile layer 10. Although not shown a backing layer may alsobe provided. Because the elastic fibers 20 are adhered to the sideopposite of the textile layer 10, this allows the stretch film comprisedof the functional layer 40 and elastic fibers 20 to be used with a widevariety of textile layers 10.

FIG. 6 shows a stretchable laminate 4 having a plurality of elasticfibers 20 disposed on a side of the textile layer 10 opposite of thefunctional layer 40. A second adhesive layer 32 bonds the functionallayer 40 and the textile layer 10.

FIG. 7 shows a stretchable laminate 5 having a plurality of elasticfibers 20 disposed on a textile layer 10. No functional layer isincorporated into the laminate 5. The textile layer 10 may be of amaterial that is both non-elastic and provides waterproofness and/orbreathability.

The disclosure also relates to a stretchable laminate comprising aplurality of elastic fibers disposed in a substantially parallelarrangement between a first textile layer and a second textile layer.The first and the second textile layers as well as the plurality of theelastic fibers can be any of those that have been previously described.One or both of the first and second textile layers may be of a materialthat is both non-elastic and provides waterproofness and/orbreathability.

The disclosure also relates to a stretchable laminate comprising aplurality of elastic fibers disposed in a substantially parallelarrangement on a first functional layer; optionally further comprising asecond functional layer wherein the second functional layer, if present,is disposed on the first functional layer with the plurality of elasticfibers disposed between the first and second functional layer or whereinthe second functional layer is disposed on the first functional layer onthe side opposite the plurality of elastic fibers, and wherein theplurality of elastic fibers have a fiber density of at least 7.9 fibersper centimeter. FIG. 8 shows a stretchable laminate 6 having a pluralityof elastic fibers 20 disposed on a functional layer 40. In embodimentswith no textile layer, the elastic fibers can have a fiber density of atleast 7.9 fibers per centimeter (20 fibers per inch) and up to about 40fibers per centimeter (about 100 fibers per inch). In other embodiments,the fiber density can be in the range of from 12 fibers per centimeterto 32 fibers per centimeter, or from 15 fibers per centimeter to 30fibers per centimeter.

In one embodiment, the stretchable laminates described herein may beused to fabricate whole garments. Garment may include any of outerwear,underwear, footwear, glove, headwear, and accessories. As shown in FIG.9 the laminates described herein may also be used to fabricate a portionor portions 51 of whole garments 50, such as an elbow panel, a shoulderregion, cuff region, or a side panel, etc. This may provide elasticityin regions of the garment that provide a benefit to the wearer or makethe garment more form-fitting. In some embodiments, the stretchablelaminates described herein may be used to fabricate a portion orportions of a shoe construction or a shoe insert, such as a toe portion,a shank portion, or a tongue portion. The garments as disclosed hereinmay be produced so that the functional layer faces away from a wearer,for example, the functional layer can be the outermost surface of thegarment. In other embodiments, the garment may be produced so that thetextile layer faces away from a wearer, for example, the textile layercan be the outermost surface of the garment.

Also disclosed are methods of manufacturing stretchable laminates havinga flat appearance from a plurality of elastic fibers, and one or moretextile layers, one or more functional layers, or a combination thereof.The elastic fibers are incorporated under tension into the stretchablelaminate as a separate layer to be positioned in a substantiallyparallel arrangement.

The process will now be described for producing a stretchable laminatecomprising a textile layer and a functional layer. It should beunderstood that any of the other embodiments described above can beproduced according to this method. While retaining the tension on theelastic fibers, the adhesive, the textile and the functional layers arefed through a lamination nip, and the resulting laminate is spooled ontoa roll and allowed to cure. Following curing, the laminate is unspooledand allowed to relax, thereby returning to an unstretched state.Stretchable laminates comprising three or more layers, for example, twotextile layers and one functional layer, one textile layer and twofunctional layers can also be produced using this method.

An advantage of the method is that the elastic fibers do not have to bewoven into the textile; rather, they are introduced as a separate layer.Therefore, off-the-shelf non-elastic textiles may be used in thestretchable laminate. Another advantage is that prototyping is faster,with quicker turn-out due to not having to weave or knit a textile withelastic fibers incorporated into the textile.

The details of one or more embodiments are set forth in the descriptionherein. Other features, objects, and advantages will be apparent fromthe description and from the claims. The examples below are intended tofurther illustrate certain aspects of the methods and compositionsdescribed herein, and are not intended to limit the scope of the claims.

Test Methods

It should be understood that although certain methods and equipment aredescribed below, any method or equipment determined suitable by one ofordinary skill in the art may be alternatively used.

Elongation and Recovery Test Protocol

ASTM test method D 5035-06 “Standard Test Method for Breaking Force andElongation of Textile Fabrics (Strip Method)” was used to measureelongation and recovery of the stretch laminate test specimens. Testspecimens 1″ wide×6″ long were cut along the warp direction. Elongationwas measured using an Instron® machine using a gauge length of 4″.Measurements were recorded at 4 lbf, at which point the load wasremoved. Total Elongation was defined as total increase in gauge lengthupon application of a force. % elongation was defined as percent (%)increase in gauge length upon application of a force. Calculation of %recovery was performed after removing the load, using equation givenbelow:% Recovery=100−100*(Final Length−Initial Length)/Total Elongation

Moisture Vapor Transmission Rate Test Protocol (MVTR)

MVTR is measured according to DIN EN ISO 15496 (2004). As this is astandard test used in the textile industry, reference is made to thedetailed description of the MVTR test disclosed in DIN EN ISO 15496(2004). For a description of the MVTR test, see also WO 90/04175 A1.

The basic principles are summarized as follows. The sample to be testedtogether with a highly water vapor permeable, but waterproof microporousmembrane is inserted in an annular sample support. Then, the support isimmersed in water for 15 minutes (deionized water at 23° C.) such thatthe membrane contacts the water. A cup is filled with a saturatedsolution of potassium acetate in water such as to produce a relativehumidity of 23% at the surface of the sample and is covered with asecond piece of the same waterproof microporous membrane. The cupincluding the potassium acetate solution and the second membrane isweighed and then placed on top of the sample support such that thesecond membrane contacts the sample. This leads to a transfer of watervapor through the sample from the side of the water into the cup withthe potassium acetate. After 15 minutes, the cup with the potassiumacetate is removed and its weight is determined. The same procedure iscarried out with the first and second membranes, but without the sample,in order to determine moisture vapor permeability of the test setupwithout the sample. Then, the MVTR of the sample can be determined fromthe difference of both measurements, also considering the influence ofthe two additional microporous membranes.

The moisture vapor transmission rate (MVTR) of the laminate according tothe invention was measured in accordance with EN ISO 15496 (2004) and isexpressed in g/m²/24 hr. In order to be considered as water vaporpermeable as used herein, the laminate should generally have a watervapor permeability of at least 3000 g/m²/24 hr, preferably at least 8000g/m²/24 hr and more preferably at least 12000 g/m²/24 hr. MVTR valuesmay be as high as 20000 g/m²/24 hr.

Suter Test for Liquid-proof Fabrics

The Suter Test Method was used to determine if a sample wasliquid-proof. This procedure is based generally on the description inASTM D 751-00, Standard Test Methods for Coated Fabrics (HydrostaticResistance Procedure B2). This procedure provides a low pressurechallenge to the sample being tested by forcing water against one sideof the test sample and observing the other side for indication thatwater has penetrated through the sample.

The test sample was clamped and sealed between rubber gaskets in afixture that held the sample so that water could be applied to aspecific area. The circular area to which water was applied was 4.25inches in diameter. The water was applied at a pressure of 1 psig (0.07bar) to one side of the sample. In testing laminates with one textilelayer the pressurized water was incident upon the film side.

The unpressurized side of the sample was observed visually for any signof water appearing for 3 minutes. If no water was observed the samplewas deemed to have passed the test and was considered liquid-proof. Thereported values were the average of three measurements.

Normalized Surface Roughness (Ra) Test Protocol

The face surface profile was measured using a non-contact surfaceprofilometer. 50 mm×50 mm square samples of the material to be testedwere cut, with one of the edges oriented parallel to the mean elasticfiber axis direction. The non-face side of the untensioned sample wasattached to a flat 50 mm×50 mm sample mount using a non-foam-based,double-sided tape (3M ID 7000122521) and a uniform pressure of 1.72Newtons/centimeter (N/cm). The sample mount was placed in the detectionarea, with the edges parallel to the x and y directions of travel of theprofilometer stage, and the surface profile of the sample was measuredwithin a 30 mm×30 mm area at an x-y resolution of 50 μm or smaller. Theaccuracy of the measurement was confirmed by measuring an appropriatecalibration standard using the same profilometer settings.

A face layer feature spacing for the laminate was determined by thetextile outermost layer. For wovens, the feature spacing is the averagespacing (center to center, in mm) of adjacent yarns, as shown by thewhite arrow 100 in FIG. 10A. For knits, the feature spacing is theaverage spacing (center to center, in mm) of adjacent loops, as shown bythe white arrow 100 in FIG. 10B.

A normalization procedure was applied to the surface profile to adjustfor surface roughness attributable to the textile layer's inherentroughness. This normalization procedure included only relevant textilesurface data. Non-surface features (such as holes in the textile layer)were omitted from the data. A 2-dimensional moving average of thesurface height data was calculated, using a window size of 2× the facelayer feature spacing. The normalized surface roughness (Ra) wascalculated in the direction of the mean elastic fiber axis for eachpixel row in the normalized surface profile. Examples of the normalizedsurface roughness can be seen in FIGS. 11B, 12B, 13B, 14B, 15B and 16B.The average normalized surface roughness and the maximum normalizedsurface roughness were then calculated from the normalized surfaceroughness data.

Laminate Thickness Test Protocol

The laminate thickness was measured by tensioning the laminate to itsfullest extent in the direction of the mean elastic fiber axis, yetwhere the laminate still exhibited ≥90% recovery and ≤5% reduction inwidth; placing the sample between two rigid surfaces with an area of 5cm²; and measuring the separation of the surfaces using a digitalmicrometer (Model XLI 40002, Mahr Federal Inc., Providence, R.I.) at apressure of 0.11 N/cm².

EXAMPLE 1 Inventive Stretchable Laminate

A length of 67 g/m² nylon woven material (Style 130970 (MI187R) fromMilliken & Company, Spartanburg, S.C.), a quantity of elastane fibers(120 denier, Type 902C from Invista, Wichita, Kans.), and a length ofpolyurethane-coated ePTFE membrane were obtained. The ePTFE membrane hadthe following properties: thickness=0.043 mm, density=0.41 grams percubic centimeter (g/cc), matrix tensile strength in the lengthdirection=31×10⁶ MegaPascal (MPa), matrix tensile strength in the widthdirection=93×10⁶ MPa, Bubble Point=1.5'10⁵ MPa. Polyurethane (PU) wasapplied by coating the ePTFE membrane and allowing it to at leastpartially penetrate the pores of the membrane, then cured.

The elastane fibers were loaded onto a beam and fed through two reeds,each at a spacing of 20 dents per centimeter (cm). Another polyurethanewas obtained and loaded in the printer to add adhesive dots to the ePTFEside of the polyurethane-coated ePTFE membrane. Dots of 335 microndiameter were applied at a percent area coverage of 54% to the ePTFEmembrane. The woven material was placed onto the adhesive side of themembrane, while the elastane fibers were tensioned to 250% elongationand inserted between the ePTFE membrane and woven material. The firstreed was mounted approximately 7 cm from the lamination nip, adjacent tothe woven material. The second reed was mounted approximately 15 cm fromthe lamination nip and shifted laterally with respect to the first reedby 5 cm. While retaining the tension on the elastane fibers, theresulting laminate was spooled onto a roll and allowed to cure, whichrequired approximately 2 days. Following curing, the laminate wasunspooled and allowed to relax, thereby returning to an unstretchedstate.

The surface topography of the outermost surface of the laminate is shownin FIG. 11A. Normalized Ra was determined, and is shown in FIG. 11B. Thethickness of the stretched laminate was 0.252 mm, the average MVTR was133305.9 g/m²/24 hr, the Suter test result was pass/pass/pass, thepercent elongation was 60.6%, and percent recovery was 96.9%, as shownin FIG. 17 .

EXAMPLE 2 Comparative Functional Laminate

A length of 67 g/m² nylon woven material (Style 130970 (MI187R) fromMilliken & Company, Spartanburg, S.C.), a quantity of elastane fibers(120 denier, Type 902C from Invista, Wichita, Kans.), and a length ofpolyurethane-coated ePTFE membrane were obtained. The ePTFE membrane hadthe following properties: thickness=0.043 mm, density=0.41 grams percubic centimeter (g/cc), matrix tensile strength in the lengthdirection=31×10⁶ MegaPascal (MPa), matrix tensile strength in the widthdirection=93×10⁶ MPa, Bubble Point=1.5×10⁵ MPa. Polyurethane (PU) wasapplied by coating the ePTFE membrane and allowing it to at leastpartially penetrate the pores of the membrane, then cured.

The elastane fibers were loaded onto a beam and fed through one reedhaving a spacing of 20 dents per centimeter (cm). Another polyurethanewas loaded in the printer to add adhesive dots to the ePTFE side of thepolyurethane-coated ePTFE membrane. Dots of 335 micron diameter wereapplied at a percent area coverage of 54% to the ePTFE membrane. Thewoven material was placed onto the adhesive side of the membrane, whilethe elastane fibers were tensioned to 250% elongation and insertedbetween the ePTFE membrane and woven material. The reed was mountedapproximately 15 cm from the lamination nip, adjacent to woven material.While retaining the tension on the elastane fibers, the resultinglaminate was spooled onto a roll and allowed to cure, which requiredapproximately 2 days. Following curing, the laminate was unspooled andallowed to relax, thereby returning to an unstretched state.

The outermost surface of the laminate is shown in FIG. 12A and visiblebuckling is shown. When the normalized Ra was determined, and is shownin FIG. 12B, there were peaks that exceeded 25 micrometers and thisconfirms the presence of buckling. The buckling is a result of the poorfiber spacing. The thickness of the stretched laminate was 0.238 mm, theaverage MVTR was 12199.9 g/m²/24 hr, the Suter test result waspass/pass/pass, the percent elongation was 55.6%, and percent recoverywas 96.3%, as shown in FIG. 17 .

EXAMPLE 3 Inventive Stretchable Laminate

A length of 146 g/m² polyester woven material (Style 758680 (US440) fromMilliken & Company, Spartanburg, S.C.), a quantity of elastane fibers(300 denier, Type 902C from Invista, Wichita, Kans.), and a length ofpolyurethane-coated ePTFE membrane were obtained. The ePTFE membrane hadthe following properties: thickness=0.043 mm, density=0.41 grams percubic centimeter (g/cc), matrix tensile strength in the lengthdirection=31×10⁶ MegaPascal (MPa), matrix tensile strength in the widthdirection=93×10⁶ MPa, Bubble Point=1.5×10⁵ MPa. Polyurethane (PU) wasapplied by coating the ePTFE membrane and allowing it to at leastpartially penetrate the pores of the membrane, then cured.

The elastane fibers were loaded onto a beam and fed through two reeds,each at a spacing of 20 dents per centimeter (cm). Another polyurethanewas obtained and loaded in the printer to add adhesive dots to the ePTFEside of the polyurethane-coated ePTFE membrane. Dots of 335 microndiameter were applied at a percent area coverage of 54% to the ePTFEmembrane. The woven material was placed onto the adhesive side of themembrane, while the elastane fibers were tensioned to 250% elongationand inserted between the ePTFE membrane and woven material. The firstreed was mounted approximately 7 cm from the lamination nip, adjacent tothe woven material. The second reed was mounted approximately 15 cm fromthe lamination nip and shifted laterally with respect to the first reedby 5 cm. While retaining the tension on the elastane fibers, theresulting laminate was spooled onto a roll and allowed to cure, whichrequired approximately 2 days. Following curing, the laminate wasunspooled and allowed to relax, thereby returning to an unstretchedstate.

The surface topography of the outermost surface of the laminate is shownin FIG. 13A. Normalized Ra was determined, and is shown in FIG. 13B. Thethickness of the stretched laminate was 0.470 mm, the average MVTR was12490.5 g/m²/24 hr, the Suter test result was pass/pass/pass, thepercent elongation was 34.4%, and percent recovery was 96.5%, as shownin FIG. 17 .

EXAMPLE 4 Comparative Functional Laminate

A length of 146 g/m² polyester woven material (Style 758680 (US440) fromMilliken & Company, Spartanburg, S.C.), a quantity of elastane fibers(300 denier, Type 902C from Invista, Wichita, Kans.), and a length ofpolyurethane-coated ePTFE membrane were obtained. The ePTFE membrane hadthe following properties: thickness=0.043 mm, density=0.41 grams percubic centimeter (g/cc), matrix tensile strength in the lengthdirection=31×10⁶ MegaPascal (MPa), matrix tensile strength in the widthdirection=93×10⁶ MPa, Bubble Point=1.5×10⁵ MPa. Polyurethane (PU) wasapplied by coating the ePTFE membrane and allowing it to at leastpartially penetrate the pores of the membrane, then cured.

The elastane fibers were loaded onto a beam and fed through one reedhaving a spacing of 13 dents per centimeter (cm). Another polyurethanewas loaded in the printer to add adhesive dots to the ePTFE side of thepolyurethane-coated ePTFE membrane. Dots of 500 micron diameter wereapplied at a percent area coverage of 39% to the ePTFE membrane. Thewoven material was placed onto the adhesive side of the membrane, whilethe elastane fibers were tensioned to 250% elongation and insertedbetween the ePTFE membrane and woven material. The reed was mountedapproximately 15 cm from the lamination nip, adjacent to woven material.While retaining the tension on the elastane fibers, the resultinglaminate was spooled onto a roll and allowed to cure, which requiredapproximately 2 days. Following curing, the laminate was unspooled andallowed to relax, thereby returning to an unstretched state.

The outermost surface of the laminate is shown in FIG. 14A and visiblebuckling is shown. When the normalized Ra was determined, and is shownin FIG. 14B, there were peaks that exceeded 25 micrometers and thisconfirms the presence of buckling. The buckling is a result of the poorfiber spacing.

EXAMPLE 5 Comparative Functional Laminate

A length of 88 g/m² nylon woven material (Style 7820 (NUERO058P) fromToray Textiles Europe Ltd, Crown Farm Way, Forest Town, Mansfield NG19OFT, United Kingdom), a quantity of elastane fibers (120 denier, Type902C from Invista, Wichita, KS), and a length of polyurethane-coatedePTFE membrane were obtained. The ePTFE membrane had the followingproperties: thickness=0.043 mm, density=0.41 grams per cubic centimeter(g/cc), matrix tensile strength in the length direction=31×10⁶MegaPascal (MPa), matrix tensile strength in the width direction=93×10⁶MPa, Bubble Point=1.5×10⁵ MPa. Polyurethane (PU) was applied by coatingthe ePTFE membrane and allowing it to at least partially penetrate thepores of the membrane, then cured.

The elastane fibers were loaded onto a beam and fed through one reedhaving a spacing of 20 dents per centimeter (cm). Another polyurethanewas obtained and loaded in the printer to add adhesive dots to the ePTFEside of the polyurethane-coated ePTFE membrane. Dots of 500 microndiameter were applied at a percent area coverage of 39% to the ePTFEmembrane. The woven material was placed onto the adhesive side of themembrane, while the elastane fibers were tensioned to 250% elongationand inserted between the ePTFE membrane and woven material. The reed wasmounted approximately 15 cm from the lamination nip, adjacent to wovenmaterial. While retaining the tension on the elastane fibers, theresulting laminate was spooled onto a roll and allowed to cure, whichrequired approximately 2 days. Following curing, the laminate wasunspooled and allowed to relax, thereby returning to an unstretchedstate.

The surface topography of the outermost surface of the laminate is shownin FIG. 15A. Normalized Ra was determined, and is shown in FIG. 15B. Thethickness of the stretched laminate was 0.388 mm, the average MVTR was11830.2 g/m²/24 hr, the Suter test result was pass/pass/pass, thepercent elongation was 70.1%, and percent recovery was 97.6%, as shownin FIG. 17 .

EXAMPLE 6 Inventive Functional Laminate

A length of 92 g/m² polyester knit material (Style 45627 (PIQE001MO)from MYBE Srl, Via alla Selva 596, Cassina Rizzardi, Italy), a quantityof elastane fibers (120 denier, Type 902C from Invista, Wichita, Kans.),and a length of polyurethane-coated ePTFE membrane were obtained. TheePTFE membrane had the following properties: thickness=0.043 mm,density=0.41 grams per cubic centimeter (g/cc), matrix tensile strengthin the length direction=31×10⁶ MegaPascal (MPa), matrix tensile strengthin the width direction=93×10⁶ MPa, Bubble Point=1.5×10⁵ MPa.Polyurethane (PU) was applied by coating the ePTFE membrane and allowingit to at least partially penetrate the pores of the membrane, thencured.

The elastane fibers were loaded onto a beam and fed through two reeds,each at a spacing of 20 dents per centimeter (cm). Another polyurethanewas loaded in the printer to add adhesive dots to the ePTFE side of thepolyurethane-coated ePTFE membrane. Dots of 335 micron diameter wereapplied at a percent area coverage of 54% to the ePTFE membrane. Thewoven material was placed onto the adhesive side of the membrane, whilethe elastane fibers were tensioned to 250% elongation and insertedbetween the ePTFE membrane and woven material. The first reed wasmounted approximately 7 cm from the lamination nip, adjacent to thewoven material. The second reed was mounted approximately 15 cm from thelamination nip and shifted laterally with respect to the first reed by 5cm. While retaining the tension on the elastane fibers, the resultinglaminate was spooled onto a roll and allowed to cure, which requiredapproximately 2 days. Following curing, the laminate was unspooled andallowed to relax, thereby returning to an unstretched state.

The flat surface topography of the outermost surface of the laminate isshown in FIG. 16A. Normalized Ra was determined, and is shown in FIG.16B. The thickness of the stretched laminate was 0.757 mm, the averageMVTR was 12359.8 g/m²/24 hr, the Suter test result was pass/pass/pass,the percent elongation was 74.9%, and percent recovery was 93.3%, asshown in FIG. 17 .

EXAMPLE 7 Maximum Fiber Spacing

FIG. 18 shows the maximum fiber spacing for different stretchablelaminates having different thickness: 0.25 mm, 0.39 mm, 0.47 mm, and0.76 mm. The fiber spacing was varied between 0.01 and 1.4 mm. Threetrendlines are shown for different maximum fiber spacing: 3.0, 2.5 and2.0. Laminates having buckling (Ra>25) are shown by X, while those beingsubstantially free of buckling (Ra<=25) are shown by dots.

EXAMPLE 8 Inventive Stretchable Laminate

Two lengths of 88 g/m² nylon woven material (Style 7820 (NUERO058P) fromToray Textiles Europe Ltd, Crown Farm Way, Forest Town, Mansfield NG19OFT, United Kingdom) and a quantity of elastane fibers (120 denier, Type902C from Invista, Wichita, Kans.) were obtained.

The elastane fibers were loaded onto a beam and fed through two reeds,each at a spacing of 20 dents per centimeter (cm). A polyurethane wasobtained and loaded in the printer to add adhesive dots to the firstlength of woven material. Dots of 305 micron diameter were applied at apercent area coverage of 83% to the ePTFE membrane. The second length ofwoven material was placed onto the adhesive side of the first length ofwoven material, while the elastane fibers were tensioned to 250%elongation and inserted between the first and second woven materials.The first reed was mounted approximately 7 cm from the lamination nip,adjacent to the woven material. The second reed was mountedapproximately 15 cm from the lamination nip and shifted laterally withrespect to the first reed by 2 cm. While retaining the tension on theelastane fibers, the resulting laminate was spooled onto a roll andallowed to cure, which required approximately 2 days. Following curing,the laminate was unspooled and allowed to relax, thereby returning to anunstretched state.

The thickness of the stretched laminate was 0.466 mm and the visualsurface appearance of the laminate was virtually identical to thesurface appearance of the unlaminated woven material. The percentelongation was 41.8%, and percent recovery was 98.3%

EXAMPLE 9 Inventive Stretchable Laminate

A length of 67 g/m² nylon woven material (Style 130970 (MI187R) fromMilliken & Company, Spartanburg, S.C.), a quantity of elastane fibers(120 denier, Type 902C from Invista, Wichita, Kans.), a length ofpolyurethane-coated ePTFE membrane and a length of 37.3 g/m² polyesterknit having a loop and chevron side (Style A1012 from Glen Raven, Inc.,Glen Raven, N.C.) were obtained. Polyurethane (PU) was applied bycoating the ePTFE membrane and allowing it to at least partiallypenetrate the pores of the membrane, then cured. The coated ePTFEmembrane had a mass of 32 grams per square meter (g/m²) and thickness of0.032 mm.

Another polyurethane was obtained and loaded in the printer to addadhesive dots to the coated side of the polyurethane-coated ePTFEmembrane. Dots of 335 micron diameter were applied at a percent areacoverage of 54% to the ePTFE membrane. The chevron side of the knitmaterial was placed onto the adhesive side of the membrane. Theresulting laminate was spooled onto a roll and allowed to cure, whichrequired approximately 2 days.

The elastane fibers were loaded onto a beam and fed through two reeds,each at a spacing of 20 dents per centimeter (cm). Another polyurethanewas obtained and loaded in the printer to add adhesive dots to the ePTFEside of the polyurethane-coated ePTFE membrane and knit laminate. Dotsof 335 micron diameter were applied at a percent area coverage of 54% tothe ePTFE membrane. The woven material was placed onto the adhesive sideof the membrane and knit laminate, while the elastane fibers weretensioned to 250% elongation and inserted between the ePTFE membrane andwoven material. The first reed was mounted approximately 7 cm from thelamination nip, adjacent to the woven material. The second reed wasmounted approximately 15 cm from the lamination nip and shiftedlaterally with respect to the first reed by 5 cm. While retaining thetension on the elastane fibers, the resulting laminate was spooled ontoa roll and allowed to cure, which required approximately 2 days.Following curing, the laminate was unspooled and allowed to relax. Theuntensioned laminate was then placed in an oven at 170° C. for 60 s,allowing additional relaxation.

The thickness of the stretched laminate was 0.398 mm and the visualsurface appearance of the laminate on the woven side was virtuallyidentical to the surface appearance of the unlaminated woven material.The percent elongation was 31.4%, and percent recovery was 99.8%.

What is claimed is:
 1. A stretchable laminate comprising: (a) a textilelayer having a first surface and a second surface; (b) a fiber layerdisposed on the first surface of the textile layer, (i) wherein thefiber layer comprises a plurality of elastic fibers, (ii) wherein theplurality of elastic fibers are disposed in a substantially parallelarrangement on the first surface of the textile layer, and (iii) whereinat least 80% of the plurality of elastic fibers have an adjacent fiberspacing distance that is less than 2.5 times a thickness of thestretchable laminate in a stretched state; and (c) a functional layerdisposed on a surface of the fiber layer opposite to the textile layer,wherein the functional layer comprises a waterproof and breathablemembrane; wherein the stretchable laminate has an elasticity greaterthan an elasticity of the textile layer, wherein the stretchablelaminate has a recovery of at least 80% after an elongation of at least10% in a direction of the elastic fibers, and wherein the second surfaceof the textile layer is substantially free of buckling.
 2. Thestretchable laminate of claim 1 wherein a maximum distance betweenadjacent fibers does not exceed 2.5 times the thickness of thestretchable laminate in a stretched state.
 3. The stretchable laminateof claim 1 wherein the plurality of elastic fibers are spaced apart atan internal distance from 0.1 to 1.5 mm.
 4. The stretchable laminate ofclaim 1 further comprising an adhesive layer disposed between (1) theplurality of elastic fibers and (2) either (a) the textile layer or (b)the functional layer.
 5. The stretchable laminate of claim 1 wherein amaterial of the textile layer has an elongation of less than 15% whenmeasured according to ASTM test method D 5035-06.
 6. The stretchablelaminate of claim 1 wherein the textile layer is a non-elastic material.7. The stretchable laminate of claim 1 wherein a material of the textilelayer comprises at least one of cotton, silk, cellulose, wool,polyamides, polyolefins, polyacrylates, polyesters, polyurethanes,fluoropolymers, copolymers or a combination thereof.
 8. The stretchablelaminate of claim 1 wherein the functional layer comprises at least oneof a fluoropolymer, polyurethane, copolyether-ester, polyolefin,polyester, or a combination thereof.
 9. The stretchable laminate ofclaim 1 wherein the functional layer is an expandedpolytetrafluoroethylene membrane.
 10. The stretchable laminate of claim1 wherein the plurality of elastic fibers comprise at least one ofnatural rubber, polybutadiene, elastomeric polyolefins, polyurethanes,silicones, fluoroelastomers, elastanes, block co-polymers containingpolyesters, a polyester-polyurethane, a polyamide, or a combinationthereof.
 11. A stretchable laminate comprising: (a) a textile layerhaving a first surface and a second surface opposite the first surface;(b) a functional layer disposed on the first surface of the textilelayer, wherein the functional layer comprises a waterproof andbreathable membrane; and (c) a fiber layer disposed on the secondsurface of the textile layer, (i) wherein the fiber layer comprises aplurality of elastic fibers, (ii) wherein the plurality of elasticfibers are disposed in a substantially parallel arrangement on thesecond surface of the textile layer, and (iii) wherein at least 80% ofthe plurality of elastic fibers have an adjacent fiber spacing distancethat is less than 2.5 times a thickness of the stretchable laminate in astretched state; wherein the stretchable laminate has an elasticitygreater than an elasticity of the textile layer, wherein the stretchablelaminate has recovery of at least 80% after an elongation of at least10% in a direction of the elastic fibers, and wherein the second surfaceof the textile layer is substantially free of buckling.
 12. Astretchable laminate comprising: (a) a textile layer having a firstsurface and a second surface; (b) a functional layer disposed on thefirst surface of the textile layer, wherein the functional layercomprises a waterproof and breathable membrane; and (c) a fiber layerdisposed on a surface of the functional layer opposite to the textilelayer, (i) wherein the fiber layer comprises a plurality of elasticfibers, (ii) wherein the plurality of elastic fibers are disposed in asubstantially parallel arrangement on the surface of the functionallayer, and (iii) wherein at least 80% of the plurality of elastic fibershave an adjacent fiber spacing distance that is less than 2.5 times athickness of the stretchable laminate in a stretched state; wherein thestretchable laminate has an elasticity greater than an elasticity of thetextile layer, wherein the stretchable laminate has recovery of at least80% after an elongation of at least 10% in a direction of the elasticfibers, and wherein the second surface of the textile layer issubstantially free of buckling.
 13. The stretchable laminate of claim 12wherein the stretchable laminate further comprises a second functionallayer and wherein the plurality of elastic fibers is disposed betweenthe functional layer and the second functional layer.
 14. Thestretchable laminate of claim 13 wherein the second functional layercomprises at least one of a fluoropolymer, polyurethane,copolyether-ester, polyolefin, polyester, or a combination thereof. 15.The stretchable laminate of claim 13 wherein the functional layer andthe second functional layer are expanded polytetrafluoroethylenemembranes.